Antimicrobial treatment of fibre products with phenylthioureas

ABSTRACT

Beta -Chlorallylthioureas as well as their derivatives obtained by adding Cl2 or Br2 at the chlorallyl group are effective microbicides. They may be used as active agents in detergents or for the purpose of imparting to fibrous materials anti-microbial and anti-mycotic resistance as well as for controlling plantpathogenic bacteria and fungi.

mafia/1332 0 '7 v 7 I United State [i 11 3,811,932

Hubele 1 1 May-21, 1974 1 ANTIMICROBIAL TREATMENT OF FIBRE 3,501,341 3/1970 Spange et al. 252/s.s x PRODUCTS w PHENYLTHIOUREAS 3,546,344 12/1970 Martin et a1. 424/322 I 3,644,204 2/1972 Heins et al 252/8.8 Inventor: Adolf Hubele, Rlehen. Switzerland 3,689,550 9/1972 Schellenbaum et al 117/1385 x [73] Assignee: Ciba-Geigy AG, Basle, Switzerland 9 [22] FiledZ May 8 1972 FOREIGN PATENTS OR APPLICATIONS 1,138,714 l/l969 Great Britainw; 424/322 [21] Appl. No.: 250,939

Related US. Application Data [62] Division of Ser. No. 34.594, May 4. 1970. [hammer-Herbert Guyn" abandoned Attorney, Agent, or F1rm-Harry Goldsmith [30] Foreign Application Priority Data May 7, 1969 Switzerland 7008/69 July 25, 1969 Switzerland 11440/69 [57] ABSTRACT [52] US. Cl 117/1385, 106/15 R, 252/8.8, ,B-Chlorallylthioureas as well as their derivatives ob- 252/106, 252/107, 260/552 R, 424/322 tained by adding C1 or Br at the chlorallyl group are [51] Int. Cl. A611 13/00, D06m 13/40 effective microbicides. They may be used as active [58] Field of Search 252/8.8; 1 17/1385; agents in detergents or for the purpose of imparting t0 424/322 fibrous materials anti-microbial and anti-mycotic resistance as well as for controlling plant-pathogenic bac- [56] References Cited teria and fungi.

UNlTED STATES PATENTS 3,033,704 5/1962 Sherrill et a1. 252/106 X 16 Claims, No Drawings ANTIMICROBIAL TREATMENT OF FIBRE PRODUCTS WITH PI IENYLTHIOUREAS which also includes derivatives thereof obtained by the addition of Clg or Br at the chlorallyl group, and in which Ar represents a phenyl group which may be unsubstituted or substituted by one or more of the following residues: halogen, NO CN, SCN, alkyl or haloalkyl with up to four carbon atoms the latter group preferably being CF -CH CI, CFCI or CCl As halogens there are to be understood fluorine, chlorine, bromine or iodine, preferably chlorine and bromine.

Those compounds are preferred in which the phenyl group is substituted by not more than three of the said substituents. Expecially active compounds of the formula l are those containing substituents in the 3,4- or 3,5-positions of the phenyl nucleus. The substituents are preferably electronegative electron drawing), but this does not exclude the simultaneous presence of electroneutral substituents such as methyl, ethyl, n- 'propyl, isopropyl, n-butyl or sec.-butyl groups.

The active substances of the formula I are active against humanand plant-pathogenic bacteria and fungi.

They have a very good activity against members of the class phycomycetes, for exampe, phytopathogenic fungi such as Botrytis and Piricularia, but also against various other pathogens on corn, soya beams, maize, rice, vegetables fruit and other cultivated plants.

They are particularly active against the following species of fungi: species of Cochliobolus miyabeanus, species of Corticium, species of Cerospora, species of Alternaria, Venturia inaequalis, Podosphaera leucotricha, Uromyces phaseoli, Cercospora apii, Cercospora bericola, Cercospora musae, Piricularia sp., Erysiphe cichoriacearum, Penicillium digitatum, Sphaerotheca humuli, Diplocarpon rosae, Uncinula necator, C0ccomyces Iziemalis, Cladosporium carpophilum, Erysiphe graminis hordei, Monolinia (Sclerotinia) Laxa, Monolinia (Sclerotinia) fructicola, Piricularia oryzae, Puct'inia recondila, Puccinia coronala, Puccinia glumarum, Pm't'inia graminis trilici, Aspergillus niger, Aspergillus terreus, Rhizocmnia, Fusarium, Verlicillium. This list is not intended to be complete.

The active substances of the invention and perparations containing them also exhibit a toxic action on fungi that attack plants in the earth and some of which cause tracheomycoses, such as Fusarium cubense, Fusarium dianthi, Verricillium alboatrum and Phialophora cinerescens.

The active substances of this formula I can also serve as bacteriostatics, for example, as additions to soap, that is to say, they can be used principally in detergent and cleaning preparations.

For this purpose there have been found especially suitable the compounds of the formula in which two of the substituents R, R and R" are identical or different from each other and represent C1 or CF;,, and the third represents a hydrogen atom.

The present invention also provides biocidal preparations, which contain as active components atleast one Y thiourea of the formula I, or a derivative thereof produced by the addition of C1 or Br to the chlorallyl group, together with one or more of the following additives: solvents, dispersing agents, wetting agents, adhesives, binders or thickeners or diluents and stabilisers.

The active components can also be used in the textile field. When applied from aqueous dispersions or from solutions in organic solvents they possess an affinity for keratin fibres and can be used for protecting these fibres against attack by micro-organisms.

In the presence of protein materials, for example, blood or serum, and non-ionic, anionic or cationic organic surface-active compounds, such as are present in the form of soaps and synthetic wetting, emulsifying or washing agents, they do not lose their biocidal action. Moreover they have no objectionable odour, they are well tolerated by healthy skin and they cause no poisonous side effects towards warm blooded animals in the concentrations customarily used in disinfection.

All these properties render the detergent and cleaning preparations of this invention suitable for a very wide range of application. Thus, for example, there may be mentioned their use in the soap industry, in cosmetics, and generally in the care of the body and hygiene as disinfecting and preserving agents for a very wide variety of technical and natural products, and especially as detergent and cleaning preparations having a disinfecting and sanitizing actionin houses and in industry. For these purposes they can be used in a very wide variety of forms. As examples there may be menprotection of textile and non-textile fibrous materials and laminar structures such as films, which may be in any stage of manufacture. against micro-organisms. The treatment of fibrous materials is especially important, because it has been found that the active substances of the formula (1) when applied from an aqueous bath exhibit a substantive affinity for a very wide variety of fibrous materials.

As fibrous materials there come into consideration natural and synthetic fibres. Among natural fibres there may be mentioned, in addition to mineral fibres, for example, asbestos, more especially cellulosic fibres, such as linen, sisal, cocus, bast, and especially cotton and nitrogenous fibres, such as leather and wool. As synthetic fibrous materials there come into consideration both polycondensates such as polyadducts and polymerisa' tion products, that is to say, polymers in a wide sense, and also glass fibres. The polymer fibres may be derived from natural or synthetic polymers. Fibres of natural polymers are, for example, regenerated cellulose and cellulose dito tri-acetate. Fibres derived from synthetic polymers are, for example, fibres of polyesters, polyamides, polyurethanes, polyacrylonitrile, polyvinyl chloride and polyethylene. In this manner it is possible to impart to these fibrous materials by simple washing with a detergent or cleaning preparation of the invenw tion a finish that is lastingly biocidal, preferably antibacterial and anti-mycotic, and thus to protect these materials against attack by micro-organisms and other pests. Fibrous materials having a finish of this kind are not only themselves protected against attack by microorganisms and moulds. They also protect their immediate surroundings and thus prevent, for example, theoccurrence of unpleasant body and perspiration odours caused by micro-organisms, which is especially advantageous with fully synthetic and cellulosic textile fibrous materials. The finish so produced has a good resistance to chlorine and perborate.

The detergent and cleaning preparations of the invention contain, in addition to the active substance of the formula (1), solid or liquid additions that are suitable for this purpose. Such additions are, for example, the usual washing assistants and washing-active substances. Washing-active substances are surface-active compounds. Such surface-active compounds are, for example, soaps, that is to say, salts, especially alkali metal salts, of fattyacids of high molecular weight, or soap-free washing-active substances, for example, anion-active alkyl-aryl sulphonates, tetrapropyl-benzene sulphonates, fatty alcohol sulphonates, condensation products of fatty acids and methyl-taurine, condensation products of fatty acids with salts of oxyethane sulphonic acids, fatty acidprotein condensation products, primary alkyl sulphonates, non-ionic products, for example, condensation products of alkyl-phenols and ethylene oxides and also cation-active compounds. As washing assistants there are to be understood compounds which themselves possess no or only a small washing power, but influence the washing properties of a detergent. Thus, for example, they are able to impart an optimum pH-value to the washing liquor or to increase the dirt-tolerance capacity and the washing effect. Examples of such substances are electrolytes, for example, trisodium phosphate, sodium diphosphate, sodium carbonate, sodium bicarbonate, sodium sulphate, sodium metasilicate or water glass, cellulose glycolates, organic complex-formers (softeners), bleaching agents, optical brighteners, light protection agents, anti-oxidants, perfumes etc.

The new preparations of the invention may be in various forms depending on their mode of use, for example, in the form of solid, semi-solid or liquid soaps, in the form of pastes, powders, emulsions, suspensions, solutions in organic solvents, or sprays, powders, granulates, tablets, in capsules of gelatine or other material, or as salves.

The quantities in which the active substances of the formula (I) are used may vary within a wide range. Generally, however, i to 30 grammes per litre ofliquor produce the desired effect. The detergent and cleaning preparations generally have a content of active substance of 0.3 to percent by weight, and preferably 0.5 to 3 percent by weight.

As further ingredients the preparations of the invention may contain, depending on the purpose for which they are to be used, other biocidal substances, preferably fungicides or microbicides.

As components of the combination there may be mentioned, for example, the following active substances:

Inorganic compounds.

Copper compounds.

cuprous oxide Bordeaux mixture copper sulphate pentahydrate copper oxychloride cupric phosphate tribasic cupric sulphate basic cupric carbonate cupric dihydrazine sulphate copper ammine complexes mixture of cupric sulphate and ammonium carbonate mixture of cupric chloride and basic cupric sulphate mixture of basic cupric carbonate and zinc salt cupric zinc chromate complex (copper zinc chromate) cupric zinc cadmium calcium chromate complex cupric oleate cupric salts of fatty acids cupric naphthenate cupric salt of S-hydroxy-quinoline (oxine-copper) cupric salt of l,2-naphthoquinone-oxime-(2) cupric salt of 3-phenyl salicylate Tin and mercury compounds.

bis-(tri-n-butyltin) oxide triphenyl-tin hydroxide (fentin hydroxide) triphenyl-tin acetate (fentin acetate) bis-(tributyl-tin) succinate mercurous chloride (calomel) mercuric chloride mercuric oxide mercury zinc chromate complex mercuric lactate ethyl-mercuri chloride 2-hydroxyethyl-mercuri acetate ethyl-mercuri isothiocyanate 3-ethoxypropyl-mercuri bromide chloromethoxypropyl-mercuri acetate methoxyethyl-mercuri chloride 2methoxyethyl-mercuri silicate bis-(methyl-mercuri) sulphate bis-(methyl-mercuri) ammonium acetate ethyl-mercuri acetate 2-methoxyethyl-mercuri acetate ethyl-mercuri phosphate isopropylmethyl-mercuri acetate methyl-mercuri cyanide methyl-mercuri benzoate N-cyano-N-(methyl-mercuri)-guanidine methyl-mercuri pentachlorophenolate ethyl-mercuri 2,3-dihydroxypropyl mercaptide methyl-mercuri 8-hydroxyquinolate (Ortho LM) N-(methyl-mercuri)-1,4,5,6,7,7-hexachloro-bicyclo- [2.2.1 hept-5-en-2,3-dicarboximide N-(ethyl-mercuri)-l ,4,5,6,7,7-hexachlorobicyc1o- [2.2.1] hept-5-en-2,3-dicarboximide sodium salt of ethyl-mercuri thiosalicylate N-(ethyl-mercuri)-p-toluene sulphonic acid anilide phenyl-mercuri acetate (PAM) phenyl-mercuri propionate phenyl-mercuri triethanolammonium lactate (PAS) phenyl-mercuri urea N-(phenyl-mercuri)-1,4,5,6,7,7-hexachloro-bicyclo- [2.2.1] hept-5-en-2,3-dicarboximide phenyl-mercuri dimethyl dithiocarbamate phenyl-mercuri formamide phenyl-mercuri chloride phenyl-mercuri acetate phenyl-mercuri benzoate phenyl-mercuri borate phenyl-mercuri hydroxide phenyl-mercuri iodide basic phenyI-mercuri nitrate phenyl-mercuri monoethanolamine lactate phenyl-mercuri salicylate hydroxy-mercuri chlorophenol hydroxy-mercuri trichlorophenol hydroxy-mercuri nitrophenol N-phenyl-mercuri ethylene diamine phenyl-mercuri monoethanolammonium acetate pyridyl-mercuri acetate diphenyl-mercuri 8-hydroxyquinolate mercuric complex with organic phosphates mixture of methyl-mercuri 2,3-dihydroxypropyl mercaptide and methyl-mercuri acetate mixture of ethyl-mercuri 2,3-dihydroxypropyl mercaptide and ethyl-mercuri acetate mixture of hydroxy-mercuri chlorophenol and hydroxy-mercuri nitrophenol.

mercury cadmium organic complex Further organic metal compounds.

cadmium succinate cadmium di-n-propyl-xanthate cadmium 8-hydroxyquinolate phenylamino-cadmium acetate phenylamino-cadmium dilactate methyl-arsine sulphide zinc octoate zinc oleate Simple organic compounds (aliphatics).

formalin paraformaldehyde acrolein methyl bromide methyl isothiocyanate tetraiodo-ethylene l,3dichloropropylene and related chlorinated C hydrocarbons l-chloro-3-bromopropylene-( 1 trans-1 ,4-dibromobutylene-( 2) l,3-dichloropropylene-( l l -chloro-2-nitropropane 2-chlorol -nitropropane trichloro-nitromethane dichloro-tetrafluoro-acetone sodium salt of propionic acid calcium salt of propionic acid chlorofumaric acid bis-B-chlorethyl ester sorbic acid and its potassium salt 2-propylene-1 1 -diol acetate Z-aminobutane dodecyl-guanidine acetate '(dodine) dodecyl-guanidine phthalate a-chloracetyll ,3-aminopropionitrile a-bromacetyl-valine amide 1 ,2-dichloro- 1 methylsulphonyl)-ethylene 1,2-dichloro- 1 butylsulphonyl )-ethylene trans-1 ,2bis-(n-propylsulphonyl)-ethylene Benzene derivatives.

p-dichlorobenzene hexachlorobenzene (HCB) l,2,4,5-tetrachloro-4-nitrobenzene (tecnazene) pentachloro-nitrobenzene (quintozene) l,3,5-trichloro-2,4,6-trinitrobenzene isomeric mixture of l,3,4-trichloro-2,6- dinitrobenzene and l,2,3-trichloro-4,6- dinitrobenzene 2,4,5,6-tetrachloro-isophthalic acid nitrile 2,4-dinitrophenyl thiocyanate diphenyl (biphenyl) o-nitro-diphenyl l-chloro-2,4-dinitronaphthalene acenaphthene Phenols.

2,4,6-trichlorophenol 2,4,5-trichlorophenol 2,4,5-trichlorophenyl acetate 2,4,5-trichlorophenyl chloracetate zinc salt of trichlorophenol m-cresyl acetate 2,3,4,6-tetrachlorophenol pentachlorophenol (PCP) o-dihydroxybenzene 2,4-dioxy-n-hexyl-benzene 2-phenyl-phen0l 3,5-dibromo-salicylaldehyde 2-benzyl-4-chlorophenol 2,2-dihydroxy-5,5'-dichloro-diphenylmethane (dichlorophene) 2,2-dihydroxy-3,3,5,5,6,6'-hexachlorodiphenylmethane 2,2-dihydroxy-5,5'-dichloro-diphenyl sulphide 2,2'-dihydroxy-3,3',5,5, tetrachloro-diphenyl sulphide 2,2'-dihydroxy-3,3',5,5-tetrachloro-diphenyl phide disodium salt 4-chloro-o-phenyl-phenol 1,4-dichloro-2,S-dimethoxybenzene (chloroneb) salicyl-anilide sulbismuth salicylate trifluoromethyl-salicyl-anilide halogenated with chlorine or bromine brominated salicyl-anilide (3 ,5-dimethyl-4-chlorophenoxy )-3thanol Dinitrophenol derivatives.

2-( l-methyl-n-propyl )-4,6-dinitrophenyl-2-methyl crotonate (binapacryl) 2-( l-methyl-n-propyl)-4,6-dinitrophenyl-isopropyl carbonate (dinobuton) 2-( l-methyl-n-heptyl )-4,6-dinitrophenyl (dinocap) methyl-2,6-dinitro-4-( lethyl-hexyl)-phenyl carbonate methyl-2,6dimitro-4-(l-propyl-pentyl)- phenyl carbonate (dinocton p) 4-nonyl-2,o-dinitro-phenyl butyrate S-methyl-2-( l-methyl-n-heptyl)-4,6-dinitrophenyl thiocarbonate Aniline derivatives.

2,6-dichloro-4-nitraniline (dichloran) 2-cyanethyl-N-phenyl carbamate propynyl-N-phenyl carbamate a-(2-bromacetoxy)-acetanilide Quinone derivatives.

2,3,5,6-t etrachloro-benzoquinone-( 1,4) (chloranil) 2.3-dichloro-naphthoquinone-( 1,4) (dichlone) 2-amino3-chl0ro-naphthoquinone-(1,4) 2-chloro-3-acetylamino-naphthoquinone-( 1,4) 4-methyl-2,3,5,lO-tetrahydro-3,5,l0-trioxo-4H4-H- naphtho-(2,3,-b)-l ,4-thiazine 2,3,6,7-tetrachloro-4a,8a-epoxy-l ,2,3,4,4a,8a-

hexahydrol ,4-methanonaphthalene-5,8-dione quinone-oxime-benzyl-hydrazone (benquinox) Trichloromethylthioderivatives.

N-(trichloromethylthio)-phthalimide (folpet) N-( trichloromethylthio)-cyclohex-4-enl ,2-

dicarboximide (captan) N-( l l ,2,Z-tetrachlorethylthio)-cyclohex-4-en-l ,2-

dicarboximide (captafol) N-methane-sulphonyl-N-trichloromethylthio-pchloraniline N'-dichlorofluoromethylthio-NN-dimethyl-N'- phenyl sulphonamide (dichlofluanide) S-(2-pyridyl-l-oxide)-S'-trichloromethyl disulphide hydrochloride Organic phosphates.

0,0,0-trimethyl thiophosphate OMEtT-Ehflfilimido-phosphonothioate -amino-bis-(dimethylamido)-phosphinyl-3phenyll,2,4-triazole (triamiphos) 5-methylamino-bis-(dimethylamido)-phosphinyl-3- phenyl-l ,2,4-triazole 0.0-diethy1-0-2-pyrazinyl-phosphorthioate O-ethyl-S,S-diphenyl-dithiolphosphate O-ethyl-S-benzyl-phenyldithiophosphate 0,0-diethyl-S-benzyl-thiolphosphate Dithioca rbamates.

zinc salt of dithiocarbazinic acid sodium N-methyl-dithiocarbamate (metham) sodium N-methoxyethyl-dithiocarbamate sodium N,N-dimethyl-dithiocarbamate (DDC) ammonium N,N-dimethyl-dithiocarbamate zinc N,N-dimethyl-dithiocarbamate (ziram) iron N,N-dimethyl-dithiocarbamate (ferbam) copper N,N-dimethyl-dithiocarbamate disodium ethylene-l ,2-bis-dithiocarbamate (nabam) O-Heterocycles bis-(3,4dichloro-2(5)-furanoyl)-ether (mucochloric anhydride) 2-methoxymethyl-5-nitrofurane 5-nitro-furfuraldoxime-(2) 5-nitro-furfuryl-amidoxime-( 2) 1-oxy-3-acetyl-6-methyl-cyclohexene-( 5 )-dione- (2,4) (dehydroacetic acid) l-N-Heterocycles 3-[2-(3,S-dimethyl-Z-oxycyclohexyl)-2-hydroxyethyl]-glutarimide (cycloheximide) phthalimide pyridine-Z-thioll -oxide or thione zinc salt of pyridine-Z-thiol-l-oxide manganous'salt of pyridine-2-thioll -oxide 8- l l-oxid0-2-pyridyl )-isothiuronium chloride l-hydroxypyridine-2- a, a-bis-(4-chlorophenyl)-3-pyridine-methanol (parinol) 8-hydroxyquinoline (8-quinolinol) 8-hydroxyquinoline sulphate (chinosol) benzoyl-S-hydroxyquinoline salicylate 3-(2-methyl-piperidino)-propyl-3,4-

dichlorobenzoate 6-ethoxyl ,2-dihydro-2,2,4-trimethyl-quinoline (ethoxyquin) Nlauryl-isoquinoline bromide 9-(p-n-hexyloxyphenyl l O-methyl-acridinium chloride 9-( p-n-hexyloxyphenyl l O-methyl-acridinium ptoluene sulphonate 2- and B-N-Heterocycles Z-n-heptadecylimidazolidine acetate (glyodine) l-hydroxyethyl-2-heptadecyl-imidazolidine l-phenyl-3 ,5-dimethyl-4-nitrosopyrazole l-p-chlorphenyl-3 ,5-dimethyl-4-nitrosopyrazole 9 l-p-sulphamylphenyl-3 ,5 -dimethyl-4-nitrosopyrazole N-( butylcarbamoyl S-Heterocycles -chloro-4-phenyl-l ,2-dithiol-3-one 2,3-dicyanol ,4-dithia-anthraquinone (dithianone) 2-( 4-thiazolyl )-benzimidazole NO-. NS- and OS-Heterocycles 4-( 2-chlorophenyl-hydrazono )-3-methyl-5- isoxazolone (drazoxolone) thiazolidinone-4-thione-(2) (Rhodanine) 3-(pchlorophenyl)-5-methyl-rhodanin 3 ,S-dimethyltetrahydro-l ,3 ,5'thiadiazine-2-thione (dazomet) 3,3-ethylene-bis-(tetrahydro-4,6-dimethyl)-2H- l,3,5-thiadazine-2-thione (milneb) 3-benzylidene-amino-4-phenyl-thiazoline-Z-thione zinc salt of 6-chlorobenzthiazole-Z-thiol 6-B-diethylamino-ethoxy-2-dimethylaminobenzthiazole dihydroehloride monoethanolammonium-benzthiazole-2-thiol lauryl-pyridinium-5 chloro-2-mercaptobenzthiazole zinc and sodium salts of 2-mercaptobenzthiazole and dimethyl-dithiocarbamate o-(fl-diethylaminoethoxy)-2- dimethylaminobenzthiazole dihydrochloride 3-trichloromethylthio-benzothiazolone 3-trichloromethylthio-benzoxazolone 3-(trichloromethyl )-5-ethoxy-l ,2,4-thiadiazole 6-methyl-2-oxol ,3-dithiolo [4,5-b]-quinoxaline (quinomethionate) 2-thio-l,3-dithiolo [4,5-b1-quinoxaline (thioquinox) 2,3-dihydro-5-carboxanilido-6-methyll ,4-oxathine 3,3 4,4-tetrachlorotetrahydrothiophene-l l -dioxide 2 ,3-dihydro-5-carboxanilido-6-methyll ,4-oxathine- 4,4-dioxide Quaternary ammonium compounds cetyl-trimethylammonium bromide n-alkyl(C CmC )-dimethylbenzyl-ammonium chloride alkenyl-dimethylethylammonium bromide dialkyldimethylammonium bromide alkyldimethylbenzylammonium chloride alkyl C -C tolylmethyltrimethylammonium chloride di-isobutylcresoxyethoxyethyldimethylbenzylammonium chloride p-di-isobutylphenoxyethoxyethyldimethylbenzylammonium chloride benzoyltrimethylammonium bromide Fungicidal antibiotics gliotoxin 2,4-diguanidino-3,5,6-trihydroxycyclohexyl-S- deoxy-2-O-(2-deoxy-2-methylamino-a-L- glucopyranosyl)3-C-formyl-B-L- lyxopentanofuranoside (streptomycin) 7-chloro-4,6-dimethoxycumaran-3-one-2-spiro-l (2 -methoxy-6 -methylcyclo hex-2 -en-4 one (griseofulvin) 4-dimethylamino-1,4,4a,5 ,Sa,

6,1l,l2a-octahydro-3,5,6,10,12,120:- hexahydroxy-6-methyl-l ,1 l-dioxo-2-naphthace'ncarboximide (Oxytetracyclin) 7-chlor-4-dimethylamino-1 ,4,4a,5 ,5a,6,l l ,1 2aoctahydro-3,6,l0, l 2,1 2a-pentahydroxy-6-methyll ,l l-dioxo-2-naphthacencarboximide (chlorotetracyclin) (pimaricin) (lancomycin) (phleomycin) (kasugamycin) (phytoactin) D(-)-threo-2,2-dichloro-N-[B-hydroxy-a' (hydroxymethyl)-p-nitrophene-ethyllacetamide (Chloramphenicol) Blasticidin-S-benzylamino-benzene sulphonate Various N-(3-nitrophenyl)-itaconimide phenoxy-acetic acid sodium p-dimethylamino-benzene diazosulphonate acrolein-phenylhydrazone 2-chloracetaldehyde-( 2,4-dinitrophenyl )-hydrazone 2-chlor-3-(tolylsulphonyl)-propionitrile l-chlor-2-phenyl-pentan-diol-(4,5 )-thione-( 3) p-nonylphenoxypolyethylene-oxyethanol-iodine v complex (a-nitromethyl)-o-chlorobenzylthioethylamine drochloride 3-(p.-t.-butyl-phenylsulphonyl)-acrylonitrile octachlorocyclohexenone pentachlorobenzyl alcohol pentachlorobenzyl acetate pentachlorobenzaldehyde cyanhydrin 2-norcamphane-methanol 2,6-bis-(dimethylaminomethyl)-cyclohexanone decachloroctahydro- 1 ,3,4-metheno-2H- cyclobutalcd]-pentalen-2-one l-( 3-chlorallyl )-3 ,5 ,7-triazal -azonia-adamantan chloride coal tar and blast furnace tar Mixtures mixture nickelsulphate-maneb mixture maneb-mercaptobenzthiazole mixture zineb-mercaptobenzthiazole mixture zineb-nickelous chloride mixture zineb nickelous sulphate mixture ziram-basic copper sulphate mixture ziram-zinc-mercaptobenzthiazole mixture thiram-cadmium chloride hydrate mixture thiram-hydroxy-mercury chlorophenol mixture thiram-phenyl-mercuri acetate 1 1 mixture polyethylene-bis-thiuramsulphide-copper oxychloride mixture methylarsine-bis-(dimethyldithiocarbarn ate )-ziram-thiram mixture folpet-phenyl-mercuri acetate mixture dodine-ferbam-sulphur mixture dithianone-copper oxychloride mixture dich1one-ferbam-sulphur mixture dinocap-dinitroocty1phenol mixture captan-quintozene-tribasic copper sulphate mixture cadmium propionate-pheny1-mercuri propionate formaldehyde-urea mixture mixture phenylammonium cadmium dilactatephenyl-mercuri formamide mixture basic copper sulphate-zinc salts.

The new thioureas of the formula (l) can be made in a simple manner by reacting a reactive derivative of a thiocarbonic acid, for example thiophosgene, with an aniline of the formula Ar-NH which is substituted as indicated in connection with formula I, and with the amine of the formula the reactions being carried out in either order of succession.

For example, thiophosgene may be reacted with the aniline and the resulting isothiocyanate, ArN=C=S, reacted with the amine of the formula 111.

In the reverse order of succession a reactive derivative of the thiocarbonic acid may be reacted with an amine of the formula 111, and the resulting isothiocyanate of the formula reacted with the aforesaid aniline.

In a more simple and known manner the isothiocyanate of the formula IV may be prepared by reacting 2,3-dich1oro-propylene-( 1) with an inorganic thiocyanate, preferably an alkaline metal or ammonium thiocyanate. 1f desired the chlorallyl group may be saturated with C1 or Bl'g either before or after the formulation of the thiourea grouping.

The following examples illustrate the invention, the parts being by weight:

Example 1 Manufacture of 185 parts of 4-ch1oro-3-trif1uoromethyl-ani1ine in 200 parts by volume of acetonitrile are added to 134 parts of [Ii-chlorallyl] -isothiocyanate in 200 parts by volume of toluene and 0.1 part of triethylene diamine. After heating the mixture for 20 hours at 80C it is evaporated in vacuo to about 400 parts by volume then diluted with petroleum ether (boiling at 50 70C),

R R, R R, R Melt- Compound ing at No "C 2 H C1 Cl H H 81 83" 3 H H H H H 93 95 4 H C,H,-, H H H 74 76 5 H CH H H H 86 87 6 H CF H H H 79 81 7 H CF H CF, H 124 127 8 CH Cl H H H 107 108 9 C1 H NO, H H 135 137 10 Br H CH H Br 140- 141 11 H H C1 H H 97 98 12 H C1 H H H 101 103 13 H Cl CH H H 92 93 14 H N0 Cl H H 114-117 15 C1 H C1 C1 H 125 126 16 C1 H H C1 H 115 116 17 H H (2 H, H H 113-114 18 C1 C1 H H H 121 122 19 Cl H C1 H H 131 132 20 H C1 H C1 H 124 125 and also the two compounds Melting at -126C (with decomposition).

Melting at 161C (with decomposition) Example 2 50 parts of the active substance of the invention 20 parts of highly adsorptive silica 25 parts of Bolus alba (kaolin) 3.5 parts of sodium benzimidazole-6,3-disulphonate l-benzyl-2-stearyl- 3.5 parts of the reaction product of p.te rt.-

octylphenol and ethylene oxide. c. An emulsion concentrate Readily soluble active substances can also be formulated as emulsion concentrates in the following manner:

parts of active substance 70 parts of xylene 10 parts of a mixture obtained by mixing a reaction product of an alkyl-phenol with ethylene oxide and calcium dodecyl-benzene sulphonate. By diluting the con- 20 centrate with water to the desired concentration there is obtained an emulsion that can be sprayed.

Example 3 In a greenhouse, Zucchetti plants were grown and sprayed once prophylactically with an aqueous liquor containing 0.1 percent of the active substance. Two days later the plants so treated were infected with spores of Erysiphe cichoriacearum DC. After 12 14 days the plants treated with the test compound No. l

showed an attack of 5 percent and the plants treated with compound No. 8 showed no attack, whereas the untreated control plants suffered a 100 percent attack.

Example 4 A mixture of equal parts of quartz sand and alumina was inoculated with an aqueous suspension of conidia of F usarium oxysporum, the mixture was charged into pots, and the pots were placed in a cabinet in a greenhouse. Two days later the pots were sown with melon seeds, and then an aqueous liquor containing a quantity "of active substance No. 2 equivalent to a rate of 30 kilogrammes per hectare was poured uniformly over 14 7 Example 5 Bean plants were grown in a greenhouse and sprayed once prophylactically with an aqueous spray liquor containing 0.1 percent of an active substance of the formula 1. Two days later the plants so treated were infected with uredo spores of Uromyces phaseoli (Pets) Wint, and placed for 2 days in a moist chamber. After subsequent incubation for 10 14 days in the greenhouse the following active substances completely killed the mould:

Action (X Compound No.

9 I00; I4 100% 15 I001 16 I00)? 17 l00% In an analagous test with vine shoots as test plants and Botrytis cinerea as test mould, compounds Nos. 2l

and 22 each gave a 95 percent kill. Their action was systemic.

In an analagous test with celery (Apium grizveolens) as test plant and Septoria apii as test mould, compound Nos. 3, 4 and 5 gave a kill of 80 percent, 80 percent and 95 percent, respectively.

Example 6 The active substances of the formula (I) exhibit a remarkably strong action against grampositive bacteria, especially against staphylococci and streptococci.

The antibacterial activity was determined in dilution tests as follows:

Bacteriostasis and Bactericidic 20 mg of active substance were dissolved in 10 ml propylene glycol, of which 0.25 ml were added to 4.75 ml of sterile glucose broth, and then diluted 1 10 in small tubes. These solutions were then inoculated with a bacterium and incubated for 48 hours at 37 C (bacteriostatics). After a test period of 24 hours 1 oese (drop?) of these cultures was stroked on glucose-agar plates and incubated for 24 hours at 37 C (bactericides). After the stated periods the following limiting concentrations were measured in parts per million of the P s, ba tsriqs at s ubac e ic es H mm Bacterium No. 2 No. 7 No. 6 No. 9 No. ll No. l2

.Itishlmsmas y 2.5 2.5 30 20 20 20 E coli 20 20 30 6O 40 Asp.niger Staphaureus 2.5 0.3 5.5 3 20 25 Com u d Bacterium W hlo lll No. 15 No. 6 No. 19 No. 20 Trich.mentagrophytes IO 30 30 A 5 E.coli 3O 30 20 Asp.niger 60 Staph.aureus l0 2 20 30 0.6

- means not tested.

The pots were kept suitably moist. After 14 days 87 Example 7 percent of the sown plants in the series of test treatmetns developed healthily, whereas 6 percent developed in the untreated control pots.

Determination of the minimum inhibitingconcentration (MIC) against bacteria and moulds in the gradient plate test.

The compounds of the formula l were mixed in the form of suitable formulations (for example, as solutions in dimethyl sulphoxide) of definite concentration with warm brain heart infusion agar (bacteria) or mycophil agar (moulds). The liquid mixtures were poured onto a solidified wedge-shaped base layer of agar, and allowed to solidify.

By means of a Pasteur pipette the test organisms were applied in the form of lines perpendicularly to the gradient. After an incubation period of 24 hours at 37C (bacteria), and 72 hours at C. (moulds), the lengths of the gerrninations grown on the lines of inoculation were measured and expressed in parts per million of active substance.

5. The rnethod according to claim 1 in which, in the comound, R,, R R and R, are hydrogen, and R, is

1. A method for imparting antimicrobial and antimicotic finishes to fibrous materials comprising contacting said materials with an aqueous bath containing an effective amount of a compound of the formula 5 01 Ba -NH-li-NH-cH,-o=cm l I R: R1

in which each of R,, R R R and R is hydrogen, chlorine, bromine, nitro, alkyl of from 1 to 4 carbon atoms, or trifluoromethyl.

2. The method according to claim 1 in which, in the compound, R,, R R and R are hydrogen, and R, is trifluoromethyl.

3. The method according to claim 1 in which, in the compound, R, is chlorine, R R and R are hydrogen; and R is nitro.

4. The method according to claim 1 in which, in the compound, R,, R R and R are hydrogen, and R is chlorine.

' 10. The method according to claim 1 in which in the compound, R, and R are chlorine, and R Rgand R are hydrogen.

11. The method according to claim 1 in which said fibrous materials are textiles.

12. A method according to claim 1 in which the com- 3 pound is in which two of R R and R are chlorine or trifluoromethyl, and the other of R R and R is hydrogen.

13. The method according to claim 12 in which R, is

trifluoromethyl, R is chlorine, and R is hydrogen.

14. The method according to claim 12 in which R,

5 and R are chlorine, and R, is hyrodgen.

15. The method according to claim 12 in which R, and R are trifiuoromethyl, and R, is hydrogen.

16. The method according to claim 12 in which R,

and R are chlorine, and R is hydrogen.

i I It at 

2. The method according to claim 1 in which, in the compound, R1, R3, R4 and R5 are hydrogen, and R2 is trifluoromethyl.
 3. The method according to claim 1 in which, in the compound, R1 is chlorine, R2, R4 and R5 are hydrogen, and R3 is nitro.
 4. The method according to claim 1 in which, in the compound, R1, R2, R4 and R5 are hydrogen, and R3 is chlorine.
 5. The method according to claim 1 in which, in the comound, R1, R3, R4 and R5 are hydrogen, and R2 is chlorine.
 6. The method according to claim 1 in which, in the compound, R1, R4 and R5 are hydrogen, R2 is chlorine, and R3 is methyl.
 7. The method according to claim 1 in which, in the compound, R1, R4 and R5 are hydrogen, R2 is nitro and R3 is chlorine.
 8. The method according to claim 1 in which, in the compound, R1, R3 and R4 are chlorine and R2 and R5 are hydrogen.
 9. The method according to claim 1 in which, in the compound, R1 and R4 are chlorine, and R2, R3 and R5 are hydrogen.
 10. The method according to claim 1 in which in the compound, R1 and R3 are chlorine, and R2, R4 and R5 are hydrogen.
 11. The method according to claim 1 in which said fibrous materials are textiles.
 12. A method according to claim 1 in which the compound is
 13. The method according to claim 12 in which R2 is trifluoromethyl, R3 is chlorine, and R4 is hydrogen.
 14. The method according to claim 12 in which R2 and R3 are chlorine, and R4 is hyrodgen.
 15. The method according to claim 12 in which R2 and R4 are trifluoromethyl, and R3 is hydrogen.
 16. The method according to claim 12 in which R2 and R4 are chlorine, and R3 is hydrogen. 